Acrylonitrile

Acrylonitrile is an organic compound with the formula {{chem2|CH2CHCN}} and the structure {{chem2|H2C\dCH\sC\tN}}. It is a colorless, volatile liquid although commercial samples can be yellow due to impurities. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group ({{chem2|\sCH\dCH2}}) linked to a nitrile ({{chem2|\sC\tN}}). It is an important monomer for the manufacture of useful plastics such as polyacrylonitrile. It is reactive and toxic at low doses.

Acrylonitrile was first synthesized by the French chemist Charles Moureu in 1893.

• {{cite journal|first=C. |last=Moureu |date=1893 |url=http://babel.hathitrust.org/cgi/pt?id=uc1.31822017842394;view=1up;seq=149 |title=Contribution à l'étude de l'acide acrylique et de ses dérivés |trans-title=Contribution to the study of acrylic acid and of its derivatives |journal=Annales de chimie et de physique |series=7th |volume=2 |pages=145–212}} See especially pp. 187–189 ("Nitrile acrylique ou cyanure de vinyle (Propène-nitrile)").
• {{cite journal|first=C. |last=Moureu |date=1893 |url=http://gallica.bnf.fr/ark:/12148/bpt6k282008w/f436.image.r=BulletindelaSocieteChimiquedeParis.langFR |title=Nitrile acrylique, cyanure de vinyle (propène-nitrile)|trans-title=Acrylic nitrile, vinyl cyanide (propenenitrile) |journal=Bulletin de la Société Chimique de France |series=3rd |volume=9 |pages=424–427}} Acrylonitrile is produced by catalytic ammoxidation of propylene, also known as the SOHIO process. In 2002, world production capacity was estimated at 5 million tonnes per year,{{Ullmann | title = Acrylonitrile | first= James F. |last=Brazdil | doi = 10.1002/14356007.a01_177.pub3}}{{cite web|publisher=American Chemical Society National Historic Chemical Landmarks |title=The Sohio Acrylonitrile Process |url=http://portal.acs.org/portal/PublicWebSite/education/whatischemistry/landmarks/acrylonitrile/index.htm |archive-url=https://archive.today/20130223214113/http://portal.acs.org/portal/PublicWebSite/education/whatischemistry/landmarks/acrylonitrile/index.htm |url-status=dead |archive-date=2013-02-23 |access-date=2013-05-13 }} rising to about 6 million tonnes by 2017.{{cite journal |last1=Davey |first1=Stephen G. |title=Sustainability: Sweet new route to acrylonitrile |journal=Nature Reviews Chemistry |date=January 2018 |volume=2 |issue=1 |pages=0110 |doi=10.1038/s41570-017-0110|doi-access=free }} Acetonitrile and hydrogen cyanide are significant byproducts that are recovered for sale. In fact, the 2008–2009 acetonitrile shortage was caused by a decrease in demand for acrylonitrile.{{cite journal | first= A.|last= Tullo | title = A Solvent Dries Up | journal = Chemical & Engineering News | volume = 86 |issue= 47 | pages = 27 | doi = 10.1021/cen-v086n047.p027|year= 2008}}

:{{chem2|2 CH3\sCH\dCH2 + 2 NH3 + 3 O2 -> 2 CH2\dCH\sC\tN + 6 H2O}}

In the SOHIO process, propylene, ammonia, and air (oxidizer) are passed through a fluidized bed reactor containing the catalyst at 400–510 °C and 50–200 kPa_g. The reactants pass through the reactor only once, before being quenched in aqueous sulfuric acid. Excess propylene, carbon monoxide, carbon dioxide, and dinitrogen that do not dissolve are vented directly to the atmosphere, or are incinerated. The aqueous solution consists of acrylonitrile, acetonitrile, hydrocyanic acid, and ammonium sulfate (from excess ammonia). A recovery column removes bulk water, and acrylonitrile and acetonitrile are separated by distillation. One of the first useful catalysts was bismuth phosphomolybdate ({{chem2|Bi9PMo12O52}}) supported on silica.{{Cite journal|last=Grasselli|first=Robert K.|date=2014|title=Site isolation and phase cooperation: Two important concepts in selective oxidation catalysis: A retrospective|journal=Catalysis Today|language=en|volume=238|pages=10–27|doi=10.1016/j.cattod.2014.05.036}} Further improvements have since been made.

Various green chemistry routes to acrylonitrile are being explored from renewable feedstocks, such as lignocellulosic biomass, glycerol (from biodiesel production), or glutamic acid (which can itself be produced from renewable feedstocks). The lignocellulosic route involves fermentation of the biomass to propionic acid and 3-hydroxypropionic acid, which are then converted to acrylonitrile by dehydration and ammoxidation.{{cite journal|last1=Grasselli|first1=Robert K.|last2=Trifirò|first2=Ferruccio|s2cid=99550463|title=Acrylonitrile from Biomass: Still Far from Being a Sustainable Process|journal=Topics in Catalysis|volume=59|issue=17–18|year=2016|pages=1651–1658|issn=1022-5528|doi=10.1007/s11244-016-0679-7}} The glycerol route begins with its dehydration to acrolein, which undergoes ammoxidation to give acrylonitrile.{{cite journal|last1=Guerrero-Pérez|first1=M. Olga|last2=Bañares|first2=Miguel A.|title=Metrics of acrylonitrile: From biomass vs. petrochemical route|journal=Catalysis Today|volume=239|year=2015|pages=25–30|issn=0920-5861|doi=10.1016/j.cattod.2013.12.046}} The glutamic acid route employs oxidative decarboxylation to 3-cyanopropanoic acid, followed by a decarbonylation-elimination to acrylonitrile.{{cite journal|last1=Le Nôtre|first1=Jérôme|last2=Scott|first2=Elinor L.|last3=Franssen|first3=Maurice C. R.|last4=Sanders|first4=Johan P. M.|title=Biobased synthesis of acrylonitrile from glutamic acid|journal=Green Chemistry|volume=13|issue=4|year=2011|pages=807|issn=1463-9262|doi=10.1039/c0gc00805b}} Of these, the glycerol route is broadly considered to be the most viable, although none of these green methods are commercially competitive.

Acrylonitrile is used principally as a monomer to prepare polyacrylonitrile, a homopolymer, or several important copolymers, such as styrene-acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylate (ASA), and other synthetic rubbers such as acrylonitrile butadiene (NBR). Hydrodimerization of acrylonitrile{{cite book |last1=Ellis |first1=Paul G |title=A radiation-chemical study of the hydrodimerisation of acrylonitrile |date=1972 |publisher=Leeds University, Ph D thesis |location=UK}}{{cite journal |last1=Buxton |first1=George V. |last2=Ellis |first2=Paul G. |last3=McKillop |first3=Thomas F.W. |title=Pulse radiolysis study of acrylonitrile in aqueous solution |journal=J. Chem. Soc., Faraday Trans. 1 |date=1979 |volume=75 |page=1050|doi=10.1039/f19797501050 }} affords adiponitrile, used in the synthesis of certain nylons:

:{{chem2|2 CH2\dCHCN + 2 e- + 2 H+ -> NCCH2\sCH2\sCH2\sCH2CN}}

Acrylonitrile is also a precursor in the manufacture of acrylamide and acrylic acid.

Hydrogenation of acrylonitrile is one route to propionitrile. Hydrolysis with sulfuric acid gives acrylamide sulfate, {{chem2|CH\dCHC(O)NH2*H2SO4}}. This salt can be converted to acrylamide with treatment with base or to methyl acrylate by treatment with methanol.

The reaction of acrylonitrile with protic nucleophiles is a common route to a variety of specialty chemicals. The process is called cyanoethylation:

:{{chem2|YH + H2C\dCHCN -> Y\sCH2\sCH2CN}}

Typical protic nucleophiles are alcohols, thiols, and especially amines.{{Ullmann|doi=10.1002/14356007.a02_001|title=Amines, Aliphatic|year=2000|last1= Eller|first1=Karsten|last2=Henkes|first2=Erhard|last3=Rossbacher|first3=Roland|last4=Höke|first4=Hartmut|isbn=3527306730}} When hydrogen cyanide is used the product is succinonitrile.{{cite encyclopedia| encyclopedia = Ullmann's Encyclopedia of Industrial Chemistry| title = Nitriles| url = http://www.mrw.interscience.wiley.com/emrw/9783527306732/ueic/article/a17_363/current/html?hd=All%2Csuccinonitrile| access-date = 2007-09-10| edition = 7th}}

Acrylonitrile and derivatives, such as 2-chloroacrylonitrile, are dienophiles in Diels–Alder reactions.

Acrylonitrile is toxic with LD50 = 81 mg/kg (rats). It undergoes explosive polymerization. The burning material releases fumes of hydrogen cyanide and oxides of nitrogen. It is classified as a Class 1 carcinogen (carcinogenic) by the International Agency for Research on Cancer (IARC),[https://www.thelancet.com/journals/lanonc/article/PIIS1470-2045(24)00384-X/fulltext "Carcinogenicity of talc and acrylonitrile"]. The Lancet, Volume 25, Issue 8 (2024) and workers exposed to high levels of airborne acrylonitrile are diagnosed more frequently with lung cancer than the rest of the population.[http://www.epa.gov/chemfact/acry-fs.txt Acrylonitrile Fact Sheet (CAS No. 107-13-1)]. epa.gov Acrylonitrile is one of seven toxicants in cigarette smoke that are most associated with respiratory tract carcinogenesis.Cunningham FH, Fiebelkorn S, Johnson M, Meredith C. A novel application of the Margin of Exposure approach: segregation of tobacco smoke toxicants. Food Chem Toxicol. 2011 Nov;49(11):2921-33. doi: 10.1016/j.fct.2011.07.019. Epub 2011 Jul 23. {{PMID|21802474}} The mechanism of action of acrylonitrile appears to involve oxidative stress and oxidative DNA damage.Pu X, Kamendulis LM, Klaunig JE. Acrylonitrile-induced oxidative stress and oxidative DNA damage in male Sprague-Dawley rats. Toxicol Sci. 2009;111(1):64-71. doi:10.1093/toxsci/kfp133 Acrylonitrile increases cancer in high dose tests in male and female rats and mice[http://cpdb.thomas-slone.org/chempages/ACRYLONITRILE.html "Acrylonitrile: Carcinogenic Potency Database"]. and induces apoptosis in human umbilical cord mesenchymal stem cells.{{cite journal | last= Sun|first= X. | title = Cytotoxic effects of acrylonitrile on human umbilical cord mesenchymal stem cells in vitro | journal = Molecular Medicine Reports | volume = 9 | issue = 1|date=January 2014 | pmid = 24248151 | url = http://www.spandidos-publications.com/mmr/9/1/97 | pages = 97–102 | doi=10.3892/mmr.2013.1802| doi-access = free }}

It evaporates quickly at room temperature (20 °C) to reach dangerous concentrations; skin irritation, respiratory irritation, and eye irritation are the immediate effects of this exposure.{{Cite web|title = CDC – Acrylonitrile – International Chemical Safety Cards |publisher=NIOSH|url = https://www.cdc.gov/niosh/ipcsneng/neng0092.html|website = www.cdc.gov|access-date = 2015-07-31}} Pathways of exposure for humans include emissions, auto exhaust, and cigarette smoke that can expose the human subject directly if they inhale or smoke. Routes of exposure include inhalation, oral, and to a certain extent dermal uptake (tested with volunteer humans and in rat studies).[http://www.epa.gov/chemfact/acry-sd.txt Acrylonitrile Fact Sheet: Support Document (CAS No. 107-13-1)]. epa.gov Repeated exposure causes skin sensitization and may cause central nervous system and liver damage.

There are two main excretion processes of acrylonitrile. The primary method is excretion in urine when acrylonitrile is metabolized by being directly conjugated to glutathione. The other method is when acrylonitrile is enzymatically converted into 2-cyanoethylene oxide which will produce cyanide end products that ultimately form thiocyanate, which is excreted via urine. Exposure can thus be detected via blood draws and urine sampling.

In July 2024, the International Agency for Research on Cancer upgraded acrylonitrile's classification from 'possibly carcinogenic' to carcinogenic for humans. The Agency found sufficient evidence linking it to lung cancer.{{cite news |last1= |first1= |title=WHO agency says talc is 'probably' cancer-causing|url=https://globalnation.inquirer.net/241682/who-agency-says-talc-is-probably-cancer-causing |accessdate=July 7, 2024 |publisher= Philippine Daily Inquirer|date=July 6, 2024}}{{Cite journal |last1=Stayner |first1=Leslie T |last2=Carreón-Valencia |first2=Tania |last3=Demers |first3=Paul A |last4=Fritz |first4=Jason M |last5=Sim |first5=Malcolm R |last6=Stewart |first6=Patricia |last7=Tsuda |first7=Hiroyuki |last8=Cardenas |first8=Andres |last9=Consonni |first9=Dario |last10=Davies |first10=Laurie |last11=De Matteis |first11=Sara |last12=Felley-Bosco |first12=Emanuela |last13=Ghio |first13=Andrew J |last14=Göen |first14=Thomas |last15=Grosse |first15=Yann |date=July 5, 2024 |title=Carcinogenicity of talc and acrylonitrile |url=https://doi.org/10.1016/S1470-2045(24)00384-X |journal=The Lancet Oncology |volume=25 |issue=8 |pages=962–963 |doi=10.1016/s1470-2045(24)00384-x |pmid=38976996 |issn=1470-2045}}

In June 1974 Coca-Cola introduced the acrylonitrile/styrene 32oz Easy‐Goer plastic bottle, offering energy savings during manufacture, increased durability, and weight savings over glass.{{Cite web |date=1977-03-01 |title=Polyester Held a Winner Over Acrylonitrile in War About Soft-Drink Bottles |url=https://www.nytimes.com/1977/03/01/archives/polyester-held-a-winner-over-acrylonitrile-in-war-about-softdrink.html |access-date=2024-11-26 |work=The New York Times }} In March 1977 after a suit filed by the Natural Resources Defense Council the FDA rescinded approval of acrylonitrile bottles citing adverse effects on test animals.{{Cite web |date=1977-02-23 |title=Cancer Experts Warn of Dangers in Some Plastic Wrap Chemicals |url=https://www.nytimes.com/1977/02/23/archives/cancer-experts-warn-of-dangers-in-some-plastic-wrap-chemicals.html |access-date=2024-11-26 |work=The New York Times }} Monsanto, Coca-Cola's bottle manufacturer refuted the decision, stating “repeated tests have demonstrated that there is no detectable migration of acrylonitrile into the bottle's content.” After several appeals in court by September 1977 the FDA finalized their ban.{{Cite web |date=1977-03-08 |title=Plastic Beverage Bottles Made From Acrylonitrile Are Banned by the F.D.A.|url=https://www.nytimes.com/1977/03/08/archives/plastic-beverage-bottles-made-from-acrylonitrile-are-banned-by-the.html |access-date=2024-11-26 |work=The New York Times }}{{cite journal | title = Monsanto Loses Plastic Bottle Fight | journal = Chemical & Engineering News | volume = 55 | issue = 39|date=1977-09-26 | url = https://pubs.acs.org/doi/pdf/10.1021/cen-v055n039.p006 | pages = 6 | doi=10.1021/cen-v055n039.p006 }}

A large amount of acrylonitrile (approximately 6500 tons) leaked from an industrial polymer plant owned by Aksa Akrilik after the violent 17th August 1999 earthquake in Turkey. Over 5000 people were affected and the exposed animals had died.{{cite web |url= https://www.ttb.org.tr/msg/dergi/ocak01/9.htm|title= ENDÜSTRİYEL BİR ÇEVRE FELAKETİ: AKRİLONİTRİL|trans-title= AN INDUSTRIAL ENVIRONMENT DISASTER: ACRYLONITRILE|author=Nadi Bakırcı|date= 2001|website= |publisher= Turkish Medical Association |access-date=}} The leak was only noticed by the company 8 hours after the incident. Healthcare workers did not know about the health effects of acrylonitrile and tried to treat the victims with painkillers and IV fluids.{{cite web |url= https://tabella.org/2020/11/30/17-agustos-1999-depremi-akrilonitril-zehirlenmesi/|title= 17 Ağustos 1999 Depremi: Akrilonitril Zehirlenmesi|trans-title= 17 August 1999 Earthquake: Acrylonitrile Poisoning|author=Fatma Dalokay |date= 30 November 2020|website= Tabella|publisher= |access-date= |quote=}} One lawyer, Ayşe Akdemir, sued the company with 44 families as the plaintiffs. Aksa Akrilik was sued by 200 residents who were affected by acrylonitrile.{{cite web |url= https://mbigpara.hurriyet.com.tr/amp/haberler/iso-nun-sasirtan-cevre-odulu-aksa-nin/525904/|title=İSO'nun şaşırtan çevre ödülü Aksa'nın |author= |date=26 June 2005 |website=Hürriyet |publisher= |access-date= |quote=}} An increase in cancer cases in the area was confirmed by the Turkish Medical Association, as the cancer rate in the affected area has increased by 80%, from 1999 to April 2002. In 2003, the owner of Aksa Akrilik died from lung cancer related to acrylonitrile exposure. As of 2001, this is the largest known acrylonitrile leak.

Acrylonitrile is not naturally formed on Earth. It has been detected at the sub-ppm level at industrial sites. It persists in the air for up to a week. It decomposes by reacting with oxygen and hydroxyl radical to form formyl cyanide and formaldehyde.{{cite journal|last1=Grosjean|first1=Daniel|title=Atmospheric Chemistry of Toxic Contaminants. 3. Unsaturated Aliphatics: Acrolein, Acrylonitrile, Maleic Anhydride|journal=Journal of the Air & Waste Management Association|date=December 1990|volume=40|issue=12|pages=1664–1669|doi=10.1080/10473289.1990.10466814|bibcode=1990JAWMA..40.1664G }} Acrylonitrile is harmful to aquatic life. Acrylonitrile has been detected in the atmosphere of Titan, a moon of Saturn.{{cite news |last=Kaplan |first=Sarah |title=This weird moon of Saturn has some essential ingredients for life |url=https://www.washingtonpost.com/news/speaking-of-science/wp/2017/08/08/this-weird-moon-of-saturn-has-some-essential-ingredients-for-life/ |date=8 August 2017 |newspaper=The Washington Post |access-date=8 August 2017 }} Computer simulations suggest that on Titan conditions exist such that the compound could form structures similar to cell membranes and vesicles on Earth, called azotosomes.{{cite web |last=Wall |first=Mike |title=Saturn Moon Titan Has Molecules That Could Help Make Cell Membranes |url=https://www.space.com/37653-saturn-moon-titan-cell-membrane-molecules.html |date=28 July 2017 |work=Space.com |access-date=29 July 2017 }}{{cite journal |last=Palmer |first=Maureen Y.|display-authors=et al |title=ALMA detection and astrobiological potential of vinyl cyanide on Titan |date=28 July 2017 |journal=Science Advances |volume =3 |pages=e1700022|number=7 |doi= 10.1126/sciadv.1700022 |pmid=28782019|pmc=5533535 |bibcode=2017SciA....3E0022P}}

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{{reflist}}

• [https://web.archive.org/web/20060301161438/http://www.npi.gov.au/database/substance-info/profiles/7.html National Pollutant Inventory – Acrylonitrile]
• [http://potency.berkeley.edu/MOE.html Comparing Possible Cancer Hazards from Human Exposures to Rodent Carcinogens] {{Webarchive|url=https://web.archive.org/web/20120903053051/http://potency.berkeley.edu/MOE.html |date=2012-09-03 }}
• [http://www.epa.gov/iris/subst/0206.htm Acrylonitrile – Integrated Risk Information System], U.S. Environmental Protection Agency
• [https://www.cdc.gov/niosh/npg/npgd0014.html CDC – NIOSH Pocket Guide to Chemical Hazards – Acrylonitrile]
• [https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=standards&p_id=9992 OSHA Table Z-1 for Air Contaminants]

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Category:Vinyl compounds

Category:Fumigants

Category:IARC Group 2B carcinogens

Category:Monomers

Category:Conjugated nitriles

Category:Commodity chemicals

Category:Substances discovered in the 19th century